Continuous process for reacting organic web materials with liquefied reagents



GEBAUER-FUELNEGG ET AL CONTINUOUS PROCESS FOR REACTING ORGANIC wlJBvMATERIALS WITH LIQUEFIED REAGENTS Feb. 21, 1939.

Filed Sept. 17, 1936 2 Sheets-Sheet l l .ww

E. GEBAUER-FUELNEGG Er AL 2,147,739 CONTINUOUS PROCESS FOR REACTNGORGANIC WEB Feb. 21, 1939.

MATERIALS WITH LIQUEFIED REAGENTS 2 Sheets-Sheet 2 Filed Sept. 17, 1936Patented eb. 21, 1939 UNITED STATES PATENT OFFICE CONTINUOUS PROCESS FORREACTING OR- GANIC WEB MATERIALS WITH LIQUEFIED REAGENTS of DelawareApplication September 17, 1936, Serial No. 101,270

2 Claims.

This invention relates to a process for exposing web material toliquefied reagents at low temperature. More specifically this inventionrelates to a continuous process for reacting strips of organic materialwith liquid reagents that are normally gaseous in form and includesapparatus -for carrying out the process.

'Ihe treating of materials in sheet or web form by a continuous processis relatively simple when the treatment is eiected at ordinarytemperatures. However, the problem becomes more difficult when thetreatment involves the use of reagentswhich boil or vaporize at very lowtemperatures and when it is desirable to eiect the treatment with suchreagents in liquefied form.

For example, in the preparation of rubber-halogen compounds or rubberhydro-halogen compounds, it yis desirable to maintain the halogen orhydro-halide reagents in liquefied form so that the same may beintimately contacted with strips of rubber without loss of reagent.Commercial production also requires that a continuous process beutilized. Our invention makes possible the continuous reaction oforganic sheet dro-halides whereby the sheet material is exposed to orpassed through a bath of the liquefied reagent. Obviously the reactionmust be carried out at very low temperatures to maintain these reagentsin liquefied form.

-We havetherefore provided a device for continually` carrying out theprocess at low tempera- Eures without loss of reagents throughvolatilizaion.

It is` an object of this invention to provide a continuous process fortreating a sheet material with a highly 'volatile liquid reagent.

It is another object of this invention to provide a process forcontinually reacting organic sheet material with liquefied reagents thatare normally gaseous in form.

A specific object of this invention is to provide a continuous processfor producing rubber halides `and @rubber hydro-halides by reactingrubber sheets with liquefied halides of hydro-halides at lowltemperatures.

A furtherobject of this invention is 'to provide a device for treatingsheet materials with highly volatile liquid reagents without wasting theliquid reagents.

materials such as sheet rubber with liquefied hy- A furthr object ofthis invention is to provide an apparatus for continuously exposing webmaterials to liqueed reagents at low temperatures.

A still further object of this invention is to provide a reactor forcarrying out low temperature chemical reactions on organic sheetmaterials.

Other and further objects of thisinvention will be apparent from thefollowing speciiication and accompanying sheets `of drawings which forma part of this specification. i

On the drawings:

Figure 1 is a vertical cross sectional view of one formv of reactorapparatus' according to this invention.

Figure 2 is a broken enlarged sectional view taken substantially alongthe line II-II of Fig. 1 with parts in elevation.

Figure 3 is a vertical sectional view, with parts in elevation, of amodiiied form of apparatus according to this invention and illustratingthe circulating system.

Figure 4 is a sectional view taken substantially along the line IV-IV ofFig. 3 showing apparatus for accelerating the reaction by the use ofactinic light rays.

Figure 5 is an enlarged fragmentary-sectional view of a modified form ofremoval chamber which may be used in the apparatus.

Figure 6 is a sectional view of a form of triple 30 seal that may beused to close the reactor.

Asshown on the drawings: i

In Figs. 1 and 2, a U-shaped or curved immersion or reaction chamber 5,adapted to hold liquefied reagents, is formed of a bottom plate 6, topplates 1, 8 and- 9 and side plates 25 and 26. The end portions of thechamber 5 slope upwardly, as shown, so that the mid-section may be`completely iilled with reagents.

A pair of cooling devices Il and I2 are located in the sloping portionsof the chamberi. Each cooling device Il and l2 comprises headers I1 andI8 connected by a series of tubes' or pipes 20.

The cooling devices I l and i2 may be supported within the chamber 5 bymeans of flanges 22 and 23 which are attached to the side plates 25 and26 by means 'of screws 2l and 28.

Idler rollers 30 are placed at the bottom of the chamber 5 adjacent tothe sloping legs thereof for directing the sheet material through there- 50 actor as will be hereinafter described. The rollers arepreferably mounted on roller bearings 32 and 33 (Fig. 2). It should beunderstood that other directing means such, as for example, a curvedplate may beused in place of the rollers 30.

Sheet material to be treated according to this invention enters thereactor chamber 5 through the right hand sloping leg thereof between aroller assembly 34 comprising a pair of rubber rollers 35 which may bedriven by any suitable source of power (not shown). The rubber rollers35 serve to guide the sheet material into the reactor chamber 5 and alsoprevent the escape of vapors from the reactor chamber. Blocks 31 and 38of rubber, leather or other suitable material are placed at either sideof the rollers 35 in contact therewith to prevent vapors from escapingaround the peripheries of the rollers. Blocks and 4| of rubber or othersuitable material are placed at either end of the rollers 35 to preventpassage of vapors around the ends thereof. A similar assembly of rollersand blocks 43 is located at the opposite end of the reactor chamber 5 inthe top of the left hand sloping leg thereof.

An` elongated horizontal heating unit 45 is placed across the top of theU-shape reactor chamber 5 to heat the reacted sheet material to roomtemperatures and to vaporize the treating liquid therefrom. The heatingunit 45 comprises two portions and 52. The lower portion 52 is suppliedwith steam or hot water from any convenient source through openings 54and 56. The upper portion 50 is for the passage of the sheet materialover the heated chamber 52. An idler roller 58 similar in constructionand mounting to the rollers 30 guides the sheet from the roller assembly43 into the space 50. An additional roller assembly 60 similar to theassembly at 34 delivers the sheet from the space 50 to the atmospherewhere it may be wound into a roll such as 6|.

It should be understood, that the interior of the U-shaped reactionchamber 5 is formed of a corrosion resistance composition since, in manyinstances, the liquefied reagents within the re actor chamber 5 arecorrosive in nature. If desired, corrosion resistant metallic strips orbelts 62 may be trained around rollers 63 and 64 positioned in the upperportions of the sloping legs of the reactor chamber 5 and directed underthe rollers 30 for providing a support for the rubber sheetV as itpasses through the chamber. These conveyor belts or strips may be formedof tantalum which is inert to the action of the liquefied reagentstherein. The belt may be driven by the roller 63 through a suitablesource of power (not shown) connected with the shaft 65 (Fig. 2)

From the above description of Figs. 1 and 2, it is evident that thesheet or web S of organic material passes through the nip of the rollers35 into the reactor chamberl5 whereupon it is cooled by therefrigerating element therein and conveyed by the tantalum belt 62downwardly into a bath of the liquefied reagent in the mid-portion ofthe reactor chamber 5. The sheet is then directed over the rollers 30across the bottom of the reactor chamber and upwardly between the nip ofthe rollers 43. During thisgpassafge through the reactor chamber 5, thesheet has undergone a chemical change and the reacted sheet RS is nextdirected through the removal chamber 45 over the pan 52 therein whereany reagents from the reactor chamber 5 remaining on or in the sheet aregasified. The reacted sheet is then removed through the last sealbetween the rollers 60 and wound into a roll 6 I.

In the second sheet of drawings the modified form of apparatus thereonis shown as specifically adapted for the reaction of thin rubber sheetswith liquefied hydrogen chloride to produce rubber hydrochloride.

As shown in Fig. 3, rubber R is milled between rollers 69 into a thinsheet S. The sheet S passes under a slitter 10 to trim the rough edgestherefrom and then into a festooning device 1| where it is allowed tocool. The festooner 1| also permits flexibility to the feeding of thesheet S into the reactor.

The sheet S from the festooning device 1| passes under a roller 12 andthrough a .double seal located in the upper end of the sloping leg 16aof the reactor 16.

The double seal is composed of flexible metallic or rubberized strips 13and 14 adapted to scrape against the sheet S. After passing between theflexible strips 13 and 14, the sheet is directed into the nip betweenrollers 15 similar to the sealing rollers described in Fig. 1. The sheetS is then directed under cooling coils 11 similar to the coils describedin Figs. 1 and 2 and under a roll 18 into the mid-portion 1Gb. Themidportion 16h is flooded with liquefied hydrogen chloride so that thesheet passes through a bath of the liquefied reagent before enteringinto the sloping leg 16C. Upon leaving the mid-section 16h, the sheet isdirected under a roller 19 beneath cooling coils similar to the coils 11and through a double seal device composed of roller seals 8| andflexiblestrips 82 and 83.

The sheet S has now undergone a chemical change and a rubberhydro-chloride sheet R. H. results, The sheet "R. H. is directed fromthe seals 82 and 83 into an elongated HC1 removal chamber 84 having asealed pan 85 therein heated with water or steam. The sheet R. H. passesover the heated chamber 85 without coming into contact with the heatingmedium and is then directed through a seal composed of flexible strips86 from which it may be wound on a reel r81.

Refrigerant for the cooling coils 11 and 80 in the reactor 16 may besupplied from a suitable source (not shown) through a feed pipe 90 confnected with a T connection v9| from which part of the refrigerant isdirected into pipes 92 leading to the cooling coils 11 andf80 while theother part is directed through a pipe 93 leading to a hydrogen chloridecondenser,94 for liquefying the gaseous reagent fed to the reactor.

Hydrogen chloride gas is yfed from a suitable source (not shown) vintoafeedpipe 95 leading to the condenser 94. The gas is liquefied in thecondenser 94 and the liquefied reagent is directed through pipe 96 intothe sloping portion 16e oi the reactor 16. l

The exhaust refrigerant from the cooling coils 11 and 80 andfrom thecondenser 94 is directed through a pipe line l91 intothe refrigerantexhaust pipe 98 which is connected to the refrigeryating cycle (notshown).

Gasifled hydrogen chloride and air in the reactor 16 is removed throughpipes 99 and |00 connected with .the 'double seals of the reactorto apipe |0| havinga positive blower |04 therein for feeding the gas and airmixture to a recovery system (not shown) for the recovery of thehydrogen chloride gas. The removal chamber. is also exhausted `by meansof pipes |02 and` |03 connected with the removal pipe |0|.

In some instances it may be desirable to accelerate the reaction in thereactor chamber 16 by means of actinic rays. For this purpose quartztubes |06 may be `positioned in the reactor as shown in Figs. 3 an-d 4.It is known that quartz tubes will transmit light, such as ultravioletrays, freely and deflect the light` Where desired by merely rougheningthe interior surface of the tubes at the desired point. Quartz tubesprovide a source of light without heat and since the reactor 16 ismaintained at very low temperatures, heat from a light source is notdesirable. However, in some instances wherethe reaction being carriedout .is not effected at extremely low temperatures, it may beadvantageous to use direct light sources, such as mercury vapor arcs andthe like.

As shown in Fig. 4, the quartz tube |06 receives light from a shieldedoutside source4 |01. The interior of the tube |06 is roughened as atover the sheet S so that the light from the source |01 will be directeddown against the sheet to accelerate the reaction.

While the tubes |06 are shown in Fig. 3 to be inserted transverselyacross the portion 16h of the reactor, 'it should be understood thatthese tubesl may be positioned at 'many other points without departingfrom the scope of the invention. For example, quartz tubes may bepositioned between and parallel to the cooling coils 11 and 80. A quartztube or tubes may also be positioned in the removal chamber 84.

Since the removal chamber 84 is necessarily considerably elongated topermit complete removal of the hydrogen chloridegas from the rubberhydro-chloride sheet and since said sheet is .very elastic in nature, itmay be desirable to modify the removal chamber as shown in Fig. 5.

The removal chamber |09 shown in Fig. 5 is provided with a cuttingdevice ||0 to subdivide the reacted sheet emerging from the portion 16eof the reactor 15 into a plurality of sections III. A conveyor belt ||2.is entrained between rollers I3 and I4 to transmit thesections throughthe removal chambers |09. The conveyor belt I I2 may be runat higherspeeds than the rate at which the reacted sheet emerges from. thereactor so as to provide spaces between each section. Flexible seals |I5and ||6 are provided at the end of the removal chamber- |09 for sealingthe same from the atmosphere.

The gaseous hydrogen chloride and air from the removal chamber |09 maybe directed through a removal pipe I|1 into a refrigerator device IIB by`means of a. blower I|9. The hydrogen chloride is liquefied in therefrigerator ||8 and drained through a drain line 2| from which it maybe-fed into the reactor 16. `'Ihe air, freed from the hydrogen chloride,is circulatedback into the removal chamber |09 through pipe |20. Thisclosed cycle permits the use of air or other inert gas in the removalchamber so that the chamber may be completely flushed with a conveyingmedium for any gas liberated by the sheet. It should be understood thatthe hydrogen chloride gas may be removed from the conveying medium bymeans other than a refrigerator.

The use of a refrlgerating device ||0 freezes out any moisture in theconveying gas and prevents theformation of hydrochloric acid in theremoval chamber. It is obvious that the hydrogen chloride shouldpreferably remain in a dehydrated conditlon so that the corrosivehydro-` chloric acid is not formed to destroy the mateother source.

Other dehydrating means may also be used in place of the refrigeratorI8. For example, a sulphuric acid tower or trays containing calciumchloride may be inserted inV the pipe line ||1 to dehydrate the air orother conveying fluid. However, a refrigerating unit is desirable sinceit also permits a recovery of hydrogen chloride gas from the conveyingfluid.

In place of the double seal shown in Figs. 1 to 3, a form of triple sealarrangement such as is shown in Fig. 6 may be used. As shown in Fig. 6,the sheet S enters between a pair of flexible strips |25 into thereactor chamber 16. However, the sheet also passes between twoadditional seals |26 and |21. A conduit |28 is positioned between theseals |26 and I 21 for Withdrawing any HCl gas that may leak thru theseal |21.- Another conduit |29 is positioned between the seals |25 and|26 for directing dehydrated air into the space between the seals |25and |26. In this manner. a slight negative presv sure is provided inthespace between the seals .This .causes a slightinward flow of air,from the space under positive pressure into the space maintained undernegative pressure thereby preventing an outward flow of any HC1 that mayleak through the seals |21. The dehydrated air inserted through conduit|29 may be obtained from thepipe |20 (Fig. 5) if desired or from any Itis preferably in a dehydrated condition to prevent formation ofhydrochloric acid in the space between the seals |26 and |21.

In this manner there is an outward flow of dehydrated air from theportion between the seals |26 and |21 which prevents outside air fromentering into the reactor chamber and which also tends to maintain theflexible strips |26 tightly against the sheet S. It should be understoodthat this triple seal may be used in place of any of the single ordouble seals shown in Figs.. 1 to 3.

In preparing rubber hydrochloride sheets from rubber and liquefiedhydrogen chloride, it has been found that ethane serves as an excellentrefrigerant. The ethane is preferably compressed in two stages andcooled by means of an ammonia refrigerating cycle. Liquid ethane is fedto the cooling unit and condensing unit at about 130 F. The vaporizedethane is removed from the reactor and condenser. 'I'he reaction betweenthe rubber sheet and HC1 is carried out at temperatures below 121 F.which is the boiling point of HC1 at atmospheric pressure. It isobvious, of course, that other refrigerants may be used withsatisfactory results. In many instances, where the reacting agent isliquefied at temperatures not materially below zero an ordinary ammoniaor sulphur dioxide refrigerating cycle may be used.

We are aware that many changes may be made and numerous details ofconstruction may be varied through a wide range without departing fromthe principles of this invention, and.we, therefore, do not purposelimiting the patent granted hereon otherwise than necessitated by theprior art.

We claim: l

l. The improvement in the method of making rubber hydrochloride whichcomprises subject- .ing rubber to the action of hydrogen chloridethereby producing rubber hydrochloride, removing unreacted hydrogenchloride in the gaseous state from the rubber hydrochloride, coolingsaid hydrogen chloride to liquefy it and freeze out moisture, andrecirculating said hydrogen chloride to contact it with unreactedrubber.

2. In the process of making rubber hydrochloride in which rubber issubjected to the action of excess hydrogen 'chloride whereby rubberhydrochloride, unreacted' hydrogen chloride and water are obtained, thesteps which comprise removing a mixture of water and unreacted hydrogenchloride in the gaseous state from the rubber hydrochloride, coolingsaid hydrogen chloride to freeze out the water from it, andrecirculating said hydrogen chloride to contact it with unreactedrubber.

, MARIE GEBAUER-FUELNEGG, Administratrix of the Estate of Erich Gebauer-Fuelnegg, Deceased.

EUGENEy W. MOFFE'I'I. HENRY F. IRVING.

